Decorative components having an elastomeric outer surface and methods of making such components

ABSTRACT

The aromatic polyurethane elastomers of the present invention are particularly suited for methods of making objects in a mold cavity. The objects generally include an elastomeric layer formed from an aromatic polyurethane and a foam layer which is subsequently applied to the elastomer. The aromatic elastomer of the present invention lends itself to being precoated with an in-mold coating or being painted after demolding the resulting part.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to decorative components and, moreparticularly, to decorative automotive components having a moldedelastomeric outer layer. The invention also relates to methods of makingsuch decorative components.

2. Discussion of the State of the Art

A recent trend in the automobile industry has been the development ofvarious non-fabric automotive trim components. Among the known systemsfor producing decorative components are polyvinyl chloride (PVC) vacuumand rotocast systems, thermoplastic polyolefin (TPO) vacuum formedsystems, thermoplastic polyurethane (TPU) rotocast and sprayed aliphaticurethane systems generally. However, each of the foregoing systemspresent certain perceived drawbacks. For example, the known PVC vacuumform and rotocast systems are initially considered undesirable in thatPVC is considered to be difficult to recycle and environmentallyunfriendly, i.e., subject to releasing dioxins and other chlorinatedby-products upon decomposition. Further, an unnecessarily thick skin isrequired to minimize the effects of plasticizer loss over time. PVCskins, particularly those which are vacuum formed, are often stiff andhave a poor feel.

TPO vacuum formed systems are also often stiff and have a poor feel.Further, the grain definition of the resultant components are consideredto be poor in quality. Additionally, TPO skins must often be coated toimprove their resistance to scratch and mar resulting in increased costsand labor.

Accordingly, U.S. Pat. No. 5,116,577 to Dabaes et al. attempted toaddress many of the aforementioned drawbacks seen in PVC and TPOsystems, as well as certain integral skin applications by developing amethod for manufacturing mold components having a relatively lowdensity, i.e., less than 700 g/dm³. The method is said to involveapplying a layer of light stable polyurethane elastomer having apredetermined color onto a mold surface by spraying and thereafterinjecting in the space of the mold cavity while the elastomer is stilltacky a synthetic foam composition. Upon curing of both the elastomerlayer and the synthetic foam, the resultant object is removed from themold.

While the Dabaes patent arguably provides for an advancement in the art,certain perceived drawbacks are seen regarding its teachings. Forexample, the required use of a light stable aliphatic polyurethaneelastomers for the external layer of the object is believed to greatlyincrease the cost of the resulting component. Further, the resultingelastomer often requires additional treatment to achieve adhesion to aurethane foam. Other perceived drawbacks include poor color matchingwith other components, poor fogging resistance, and poor feel due to therelatively thick skins that are typically achieved in practice.

SUMMARY OF THE INVENTION

In view of the foregoing, the compositions utilized to form thedecorative components according to the methods of the present inventionare believed to offer a significant cost savings, uniform color andgloss, excellent green strength and a high grain definition. Thedecorative components also exhibit excellent softness and feel and aregenerally resistant to runs and sagging. The elastomer compositionsemployed in accordance with the teachings of the present invention arereadily processable and offer excellent adhesion to a variety ofcoatings and urethane foams used as backing layers.

According to a first aspect of the invention, a sprayable elastomercomposition is described as comprising:

the reaction product of:

a) an aromatic isocyanate;

b) a solids containing polyol selected from the group consisting ofgraft polyols, polyisocyanate polyaddition polyols, polymer polyols, PHDpolyols and mixtures thereof;

c) a polyol composition other than b); and

d) optionally one or more components selected from the group consistingof catalysts, chain extenders, defoamers, surface-active agents,adhesion promoters, flame retardants, anti-oxidants, water scavengers,dyes, ultraviolet light stabilizers, pigments, fillers, thixotropicagents and mixtures thereof;

wherein the solid contents of all components other than a) is up to 40.0weight percent.

Preferably, the reaction product will include between about 5.0 weightpercent to about 70.0 weight percent of a solid containing polyol basedon the total amount of all components other than a).

According to another aspect of the present invention, a sprayableelastomer composition is disclosed as comprising:

a) an aromatic isocyanate;

b) a polyol composition including one or more polyols selected from thegroup consisting of polyether, polyester, polytetrahydrofuran, aminefunctional polyols and mixtures thereof, said polyol having a numberaverage molecular weight of from about 100 to about 10,000;

c) optionally one or more components selected from the group consistingof catalysts, chain extenders, defoamers, surface-active agents,adhesion promoters, flame retardants, anti-oxidants, water scavengers,dyes, ultraviolet light stabilizers, pigments, fillers, thixotropicagents and mixtures thereof;

wherein said elastomer has an elongation after heat aging at 121° C. for500 hours of at least 150 percent.

According to another aspect of the invention, a method of making adecorative component in a mold cavity is disclosed as comprising thesteps of:

a) applying a first coating composition having a predetermined color tosaid mold cavity;

b) applying an aromatic elastomer composition over said coating in saidmold cavity and allowing said elastomer to cure to form an elastomericlayer; and

c) optionally demolding the resulting component.

Thereafter, either while the component remains in the mold cavity orafter removal of the decorative component, a polyurethane foamcomposition having the desired density characteristics can be applied tothe elastomeric layer to form a backing layer. Subsequent coatingapplications can also be applied over said first coating if desired.

Under an alternative method of the present invention, a decorativecomponent can be formed in a mold having a mold cavity by the steps of:

a) applying an aromatic elastomer composition over a surface of saidmold cavity and allowing said elastomer composition to at leastpartially cure to form an elastomeric layer;

b) introducing a polyurethane foam composition to said mold cavity andapplying said foam composition to said at least partially curedelastomeric layer to form a backing layer on said component; and

c) demolding the resulting component.

A coating composition can then be applied to the elastomeric layer afterthe decorative component is demolded.

Additional benefits and advantages of the present invention will becomeapparent from a reading of the description of the preferred embodimentstaken in conjunction with the specific examples provided.

DETAILED DESCRIPTION OF THE INVENTION

The aromatic elastomer composition of the present invention includes anisocyanate component a) which generally corresponds to the formula R′(NCO)_(Z) wherein R′ is a polyvalent organic radical which is aromaticand z is an integer which corresponds to the valence of R′ and is atleast 2. Representative of the types of organic polyisocyanatescontemplated herein include, for example, bis(3-isocyanatropropyl)ether, , 4-diisocyanatobenzene, 1,3-diisocyanato-o-xylene,1,3-diisocyanato-p-xylene, 1,3-diisocyanato-m-xylene,2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitro-benzene,2,5-diisochyanato-1-nitrobenzene, m-phenylene diisocyanate, p-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,mixtures of 2,4- and 2,6-toluene diisocyanate, 1,5-naphthalenediisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4′-diphenylmethanediisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, and3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; the triisocyanates suchas 4,4′,4″-triphenylmethane triisocyanate polymethylene polyphenylenepolyisocyanate and 2,4,6-toluene triisocyanate; and the tetraisocyanatessuch as 4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate.Especially useful due to their availability and properties are toluenediisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethanediisocyanate, polymethylene polyphenylene polyisocyanate, and mixturesthereof.

The polyisocyanate component is preferably a modified multivalentisocyanate, i.e., product which is obtained through chemical reactionsof the above diisocyanates and/or polyisocyanates. Examples includepolyisocyanates containing the following groups: esters, ureas, biurets,allophanates and preferably carbodiimides, uretonimines, isocyanurateand/or urethane group containing diisocyanates and/or polyisocyanates.Individual examples are: aromatic polyisocyanates containing urethanegroups, having NCO contents of from 8 to 33.6 weight percent, morepreferably of from 18 to 25 weight percent, for example with diols,triols, oxyalkylene glycols, dioxyalkylene glycols,polyoxyalkyleneglycols, polyester polyols or polytetrahydrofuran havingmolecular weights up to 6000, modified 4,4′-diphenylmethanediisocyanateor toluenediisocyanate, whereby they are able to be employedindividually or in mixtures as di- and/or polyoxyalkyleneglycols.Individual examples of the polyoxyalkyleneglycols include diethyleneglycols, dipropylene glycols, polyoxyethylene glycols, polyoxypropyleneglycols and polyoxypropylenepolyoxethylene glycols. Suitable also areprepolymers containing NCO groups, having NCO contents of from 8 to 25weight percent, more preferably of from 14 to 21 percent. Also suitableare polyisocyanates containing liquid carbodiimide-uretonimine groupsand/or isocyanurate rings, having NCO contents of from 8 to 33.6 weightpercent, more preferably from 21 to 31 weight percent, for example,based on 4,4′-2,4′- and/or 2,2′-diphenylmethanediisocyanate and/or 2,4-and/or 2,6-toluenediisocyanate and preferably 2,4- and2,6-toluenediisocyanate, as well as the corresponding isomeric mixtures4,4′-, 2,4′- and 2,2′-diphenylmethanediisocyanate, as well as thecorresponding isomeric mixtures for example from 4,4′- and2,4′-diphenylmethanediisocyanates; mixtures ofdiphenylmethanediisocyanates and polyphenylpolymethylenepolyisocyanates(polymeric MDI) and mixtures of toluenediisocyanates and crude MDI.These quasi-prepolymers are prepared by reacting an excess of organicpolyisocyanate or mixtures thereof with a minor amount of an activehydrogen containing compound as determined by the well knownZerewitinoff test as described by Kohler in Journal of the AmericanChemical Society, 49, 3181 (1927).

Most preferably used are: (i) polyisocyanates containingcarbodiimide-uretonimine groups and/or urethane groups, from4,4′-diphenylmethanediisocyanate or a mixture of 4,4′- and2,4′-diphenylmethanediisocyanates having an NCO content of from 8 to33.6 weight percent; (ii) prepolymers containing NCO groups, having anNCO content of from 8 to 27 weight percent, based on the weight of theprepolymer, prepared by the reaction of polyoxyalkylene polyols, havinga functionality of from 2 to 4 and a molecular weight of from 600 to6000 with 4,4′-diphenylmethane diisocyanate or with a mixture of 4,4′-and 2,4′-diphenylmethane diisocyanates and mixtures of (i) and (ii).

The reaction product, under a first embodiment, also includes a solidscontaining polyol b) including up to about 40.0 weight percent solidsbased on a total of all components other than the polyisocyanatecomponent. Higher solids content tends to result in viscosities whichare not suitable for sprayable elastomeric compositions, among otherperceived difficulties such as the agglomeration of the graft solids,for example.

The phrase “solids containing polyol” as used herein is intended to meanpolyether polyols including organic fillers in dispersed distribution,wherein the filler material is at least in part chemically bound to thepolyether. These so called solids containing polyols are preferablyselected from the group consisting of graft polyols, polyisocyanatepolyaddition (PIPA) polyols, polymer polyols and PHD polyols andmixtures thereof.

The graft polymer dispersions, otherwise referred to herein as graftpolyols, are generally prepared by the in situ polymerization, in thepolyols listed below, of an ethylenically unsaturated monomer or amixture of ethylenically unsaturated monomers. Representativeethylenically unsaturated monomers which may be employed in the presentinvention include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene,1,7-octadiene, styrene, α-methylstyrene, 2-methylstyrene,3-methylstyrene and 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene,isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene,benzylstyrene, and the like; substitute styrenes such as cyanostryrene,benzylstyrene, and the like; substitute styrenes such as cyanostyrene,nitrostyrene, N,N-dimethylaminostyrene, acetoxystyrene, methyl4-vinylbenziate, phenoxystyrene, p-vinylbenzoate, phenoxystyrene,p-vinylphenyl oxide, and the like; the acrylic and substituted acrylicmonomers such as acrylonitrile, acrylic acid, methacrylic acid, methylacrylate, 2-hydroxyethyl acrylate, methyl methacrylate, cyclohexylmethacrylate, benzyl methacrylate, isopropyl methacrylate, octylmethacrylate, methacrylonitrile, ethyl α-acetaminoacrylate, butylacrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butylacrylamide,methacrylyl formamide and the like; the vinyl esters, vinyl ethers,vinyl ketones, etc., such as vinyl acetate, vinyl butyrate, isopropenylacetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinylmethoxyacetate, vinyl benzoate, vinyltoluene, vinylnaphthalene, vinylmethyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butylethers, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether,3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxy diethyl ether, vinyl methylketone, vinyl ethyl ketone, vinyl phosphonates such as vinyl phenylketone, vinyl ethyl sulfone, N-methyl-N-vinyl acetamide,N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfoxide, divinylsulfone, sodium vinylsulfonate, methyl vinylsulfonate, N-vinyl-pyrrole,and the like; dimethyl fumarate, dimethyl maleate, maleic acid, crotonicacid, fumaric acid, itaconic acid, monomethyl itaconate,t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate,glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid,vinyl pyridine and the like. Any of the known polymerizable monomers canbe used and the compounds listed above are illustrative and notrestrictive of the monomers suitable for use in this invention.Preferably, the monomer is selected from the group consisting ofacrylonitrile, styrene and mixtures thereof.

The amount of ethylenically unsaturated monomer employed in thepolymerization reaction is generally from 25 percent to 70 percent,preferably from 30 percent to 50 percent, based on the total weight ofthe product. The polymerization occurs at a temperature between about25° C. and 180° C., preferably from 80° C. to 135° C.

The unsaturated polyols or macromers which may be employed in preparingthe graft polymer dispersion may be prepared by the reaction of anyconventional polyol such as those described above with an organiccompound having both ethylenic unsaturation and a hydroxyl, carboxyl,anhydride, isocyanate or epoxy group or they may be prepared byemploying an organic compound having both ethylenic unsaturation and ahydroxyl, carboxyl, anhydride, isocyanate or epoxy group or they may beprepared by employing an organic compound having both ethylenicunsaturation and a hydroxyl, carboxyl, anhydride, or epoxy group as areactant in the preparation of the conventional polyol. Representativeof such organic compounds include unsaturated mono- and polycarboxylicacids and anhydrides such as maleic acid and anhydride, fumaric acid,crotonic acid and anhydride, propenyl succinic anhydride, acrylic acid,acryloyl chloride, hydroxy ethyl acrylate or methacrylate andhalogenated maleic acids and anhydrides, unsaturated polyhydric alcoholssuch as 2-butane-1,4-diol, glycerol allyl ether, trimethylolpropaneallyl ether, pentaerythritol allyl ether, pentaerythritol vinyl ether,pentaerythritol diallyl ether, pentaerythritol vinyl ether,pentaerythritol diallyl ether, and 1-butane-3,4-diol, unsaturatedepoxides such as 1-vinyl-cyclohexene-3,4-epoxide, butadiene monoxide,vinyl glycidyl ether (1-vinyloxy-2,3-epoxy propane), glycidylmethacrylate and 3-allyloxypropylene oxide (allyl glycidyl ether).

Illustrative polymerization initiators which may be employed are thewell-known free radical types of vinyl polymerization initiators such asthe peroxides, persulfates, perborates, percarbonates, azo compounds,etc. These include hydrogen peroxide, dibenzoyl peroxide, acetylperoxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butylperoxide, lauroyl peroxide, butyryl peroxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, paramethane hydroperoxide, diacetylperoxide, di-α-cunyl peroxide, dipropyl peroxide, diisopropyl peroxide,isopropyl-t butyl peroxide, butyl-t-butyl peroxide, difuroyl peroxide,bis(triphenylmethyl) peroxide, bis(p-methoxybenzoyl) peroxide,p-monomethoxybenzoyl peroxide, rubene peroxide, ascaridol, t-butylperoxybenzoate, diethyl peroxyterephthalate, propyl hydroperoxide,isopropyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide,cyclohexyl hydroperoxide, trans-decalin hydroperoxide, α-methylbenzylhydroperoxide, α-methyl-α-ethyl benzyl hydroperoxide, tetralinhydroperoxide, triphenylmethyl hydroperoxide, diphenylmethylhydroperoxide, α,α′-azobis-(2-methyl heptonitrile),1,1′-azo-bis(cyclohexane carbonitrile), 4,4′-azo-bis(4-cyanopentanoicacid), 2,2′-azobis(isobutyronitrile), 1-t-butylazo-1-cyanocyclohexane,persuccinic acid, diisopropyl peroxydicarbonate,2,2′-azobis(2,4-dimethylvaleronitrile),2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2,2′-azobis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane,1-t-amylazo-1-cyanocyclohexane,2,2′-azobis(2,4-dimethyl-4-methoxyvaleronitrile,2,2′-azobis-2-methylbutyronitrile, 2-t-butylazo-s-cyano-4-methylpentane,2-t-butylazo-2-isocutyronitrile, to butylperoxyisopropyl carbonate andthe like; a mixture of initiators may also be used. The preferredinitiators are 2.2′-axobis(2-methylbutyronitrile),2,2′-axobis(isobutyronitrile), 2.2′-axobis(s,4-demethylvaleronitrile),2-t-butylazo-2-cyano4-methylpentane, 2-t-butylazo-2-cyano-butane andlauroyl peroxide, Generally, from about 0.1 percent to about 10 percent,preferably from about 1 percent to about 4 percent, by weight ofinitiator based on the weight of the monomer will be employed in theprocess of the invention.

By way of non-limiting example, useful commercial graft polyolformulations include Pluracol® 1198, Pluracol® 1218, Pluracol® 1409 andPluracol® 1413, each of which are available from BASF Corporation.

Polyaddition polyols as the phrase is used herein is intended to meanthe reaction product of an isocyanate and an olamine dispersed in apolyol composition. The polyaddition polyol dispersions preferably havea viscosity in the range of about 4,000 to about 50,000 mPas. Inaddition to known isocyanate components such as those noted herein, theolamine component may, for example, be any one of a number ofalkanolamines such as monoethanolamine, diethanolamine,dimethylethanolamine, triethanolanine, N-methylethanolamine,N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine,N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine,triisopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine,N-propylisopropanolamine and mixtures thereof. The choice of polyolsuitable for the dispersion in a vat and should be within the purview ofthe skilled artisans as suggested by U.S. Pat. No. 5,292,778 which ishereby incorporated by reference.

PHD polyols as the phrase is used herein is intended to mean thereaction product of an isocyanate and either a diamine or hydrazine toform polymer or polyhydrazodicarbonamide dispersions in polyol producedas a result of free radical polymerization employing olefinic monomerswith polyester serving as the base. Thus, the polymer polyols includethe grafted copolymer along with homopolymers of one or more olefinsdispersed in unaltered polyether.

For a further understanding of the PHD polyols which are useful inaccordance with the teachings of the present invention, reference can bemade to the various PHD polyols disclosed in U.S. Pat. Nos. 4,089,835and 4,260,530, both of which are fully incorporated herein by reference.

The aromatic elastomer composition according to the first embodiment ofthe present invention also comprises c) a polyol composition.Additionally, under a second embodiment of the present invention, thesprayable elastomer can be prepared using certain specified polyolsabsent any of the so called solids containing polyols. The polyolcomposition (exclusive of solids) generally includes one or more polyolcomponents which are prepared by the catalytic condensation of analkylene oxide or mixture of alkylene oxides either simultaneously orsequentially with an organic compound having at least two activehydrogen atoms, such as evidenced by U.S. Pat. Nos. 1,922,459;3,190,927; and 3,346,557. Representative polyols includepolyhydroxyl-containing polyesters and polycarbonates, polyoxyalkylenepolyether polyols such as the aforementioned polyoxyalkylene polyetherpolyols, polyhydroxy-terminated polyurethane polymers,polyhydroxyl-containing phosphorous compounds, and alkylene oxideadducts of polyhydric polythioesters, polyacetals, aliphatic polyols andthiols, ammonia and amines including aromatic, aliphatic andheterocyclic amines, as well as mixtures thereof. Alkylene oxide adductsof compounds which contain two or more different groups within theabove-defined classes may also be used, for example, amino alcoholswhich contain an amino group and a hydroxyl group. Also, alkylene oxideadducts of compounds which contain one SH group and one OH group as wellas those which contain an amino group and an SH group may be used.Generally, the number average molecular weight of the polyols will varyfrom 400 to 10,000.

Suitable hydroxy-terminated polyesters may be used such as thoseprepared, for example, from polycarboxylic acids and polyhydricalcohols. Any suitable polycarboxylic acid may be used such as oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsicacid, maleic acid, fumaric acid, glutaconic acid, αhydromuconic acid,β-hydromuconic acid, α-butyl-α-ethyl-glutaric acid, α,β-diethylsuccinicacid, isophthalic acid, therephthalic acid, hemimellitic acid and1,4-cyclohexanedicarboxylic acid. Any suitable polyhydric alcohol,including both aliphatic and aromatic, may be used such as ethyleneglycol, propylene glycol, trimethylene glycol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol,1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol,1,1,1-trimethylolpropane, 1,1,-trimethylolethane, 1,2,6-hexanetriol,α-methyl glucoside, pentaerythritol, and sorbitol. Also included withinthe term “polyhydric alcohols” are compounds derived from phenol such as2,2-bis(4-hydroxylphenyl)propane, commonly known as Bisphenol A.

The hydroxyl-containing polyester may also be a polyester amide such asis obtained by including some amine or amino alcohol in the reactantsfor the preparation of the polyesters. Thus, polyester amides may beobtained by condensing an amino alcohol such as ethanolamine with thepolycarboxylic acids set forth above or they may be made using the samecomponents that make up the hydroxyl-containing polyester with only aportion of the components being a diamine such as ethylene diamine.

Any suitable polyoxyalkylene polyether polyol may be used such as thepolymerization product of an alkylene oxide or a mixture of alkyleneoxides with a polyhydric alcohol. Any suitable polyhydric alcohol may beused such as those disclosed above for use in the preparation of thehydroxy-terminated polyesters. Suitable initiators include bothaliphatics and aromatics, such as ethylene glycol, propylene glycol,dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol,1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane,1,1,1-trimethylolethane, 1,2,6-hexanetriol, α-methyl glucoside,pentaerythritol, and sorbitol. Any suitable alkylene oxide may be usedsuch as those disclosed above for preparing the prepolymers. Examples ofalkylene oxides include ethylene oxide, propylene oxide, butylene oxide,amylene oxide, mixtures thereof, tetrahydrofuran, alkyleneoxide-tetrahydrofuran mixtures, epihalohydrins and aralkylene oxidessuch as styrene oxide. Polyethers which are particularly suitableinclude the alkylene oxide addition products of trimethylolpropane,glycerine, propylene glycol, dipropylene glycol; sucrose and blendsthereof having number average molecular weights of from 1000 to 5000.

Suitable polyhydric polythioethers which may be condensed with alkyleneoxides include the condensation product of thiodiglycol or the reactionproduct of a dicarboxylic acid such as is disclosed above for thepreparation of the hydroxyl-containing polyesters with any othersuitable thioether glycol.

Polyhydroxyl-containing phosphorous compounds which may be used includethose compounds disclosed in U.S. Pat. No. 3,639,542. Preferredpolyhydroxyl-containing phosphorous compounds are prepared from alkyleneoxides and acids of phosphorous having an acid equivalency of from about72 percent to about 95 percent.

Suitable polyacetals which may be condensed with alkylene oxides includethe reaction product of formaldehyde or other suitable aldehydes with adihydric alcohol or an alkylene oxide such as those disclosed above.

Suitable aliphatic thiols which may be condensed with alkylene oxidesinclude alkanethiols containing at least two —SH groups such as1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, and1,6-hexanedithiol; alkene thiols such as 2-butene-1,4-dithiol; andalkyne thiols such as 3-hexyne-1,6-dithiol.

Polyols having initiator molecules containing nitrogen may be used inthe elastomeric compositions of the present invention. Suitable amineswhich may be condensed with alkylene oxides include aromatic amines suchas aniline, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene,methylene dianiline, the condensation products of aniline andformaldehyde, and 2,3-, 2,6-, 3,4-, 2,5-, and 2,4-diaminotoluene (TDA)and mixtures of the isomers; and aliphatic amines such as methylamine,triisopropanolamine, ethylenediamine, 1,3-diaminopropane,1,3-diaminobutane, and 1,4-diaminobutane. Polyethers having aromaticamines as initiator molecules are also suitable.

Polyols containing ester groups can also be employed in the subjectinvention. These polyols are prepared by the reaction of an alkyleneoxide with an organic dicarboxylic acid anhydride and a compoundcontaining reactive hydrogen atoms. A more comprehensive discussion ofthese polyols and their method of preparation can be found in U.S. Pat.Nos. 3,585,185; 3,639,541 and 3,639,542,

The aromatic elastomer composition of the present invention alsooptionally includes d) one or more components selected from the groupconsisting of catalysts, chain extenders, defoamers, surface-activeagents, adhesion promoters, flame retardants, anti-oxidants, waterscavengers, dyes, ultraviolet stabilizers, pigments, fillers,thixotropic agents and mixtures thereof. As additional components c) areemployed, the total solids content may increase such that the totalsolids content of all components other than the isocyanate component a)is up to about 40.0 weight percent.

The use of chain extenders, while optional, is highly preferred.Examples of suitable chain extenders include those compounds having atleast two functional groups bearing active hydrogen atoms such as water,hydrazine, primary and secondary diamines, amino alcohols, amino acids,hydroxy acids, glycols, or mixtures thereof. Such agents will generallyhave a number average molecular weight of less than about 400. Apreferred group of chain extending agents include water, ethyleneglycol, 1,4-butanediol, glycerine and mixtures thereof.

While the amount of chain extenders employed is in large part determinedby the anticipated end use of the elastomers, in general the elastomericcomposition of the present invention will include between about 4.0 toabout 20.0% chain extender, more preferably from about 6.0 to about15.0% and still more preferably from about 8.0 to about 12.0% by weight.

The use of catalysts is highly preferred. Examples of suitableamine-based catalysts which may be used include tertiary amines such as,for example, triethylenediamine, N-methylmorpholine, N-ethylmorpholine,diethylethanolamine, N-cocomorpholine,1-methyl-4-dimethylaminoethylpiperizine, 3-methoxypropyidimethylamine,N,N,N′-trimethylisopropyl propylenediamine,3-diethylaminopropyldiethylamine, dimethylbenzylamine, and the like.Other suitable catalysts are the metal based catalysts, for example,stannous chloride, dibutyltin di-2-ethyl hexanoate, stannous oxide, aswell as other organometallic compounds including potassium, zinc,mercury and lead based catalysts. Other useful catalysts are disclosedin U.S. Pat. No. 2,846,408 which is hereby incorporated by reference.

Preferred catalysts however, are those commercially available aminecatalysts such as DABCO® EG, DABCO® HG, DABCO® 33LV and POLYCAT® 17which are commercially available from Air Products Corporation.Particularly suitable metal based catalysts are dioctyltin dimercaptincommercially available as FOMREZ® UL-32 catalyst and other tin catalystsand various BICAT® catalysts which are bismuth carboxylate, zinccarboxylate catalysts and mixtures thereof available from ShepherdChemical Company. The most preferred catalyst will be a mixture of amineand metal based catalysts.

Examples of suitable UV light stabilizers which may be used include byway of non-limiting example Tinuvin® 144, Tinuvin® 328, Tinuvin® 765,Tinuvin® 770, all of which are commercially available from CibaSpecialty Chemicals Corporation. The UV light stabilizer may be used inamounts of up to 2.0 weight % of the elastomeric composition, with 0.25weight % to about 0.75 weight % being preferred. Among the commerciallyavailable anti-oxidants which are considered useful are UVINUL® A03available from BASF Corporation and IRGANOX® 1010 and IRGANOX® 1098,each of which are available from Ciba Specialty Chemicals Corporation.The anti-oxidants, otherwise referred to herein as heat stabilizers, maybe used in amounts of up to 2.0 weight percent of the elastomericcomposition, with 0.25 weight percent to 0.75 weight percent beingpreferred.

The isocyanate component (a) and the resin component including both thepolyol component b) and optional auxiliaries c) will generally becombined in an index of from 80 to 120, and preferably an index of from90 to 110. The most preferred index for the aromatic elastomercomposition will be from 95 to 105, where 100 index refers to thestoichiometric ratio, 90 index refers to 90 percent of the isocyanaterequired for a stoichiometric ratio and so on.

The elastomer composition of the prevention may be used in a method ofmanufacturing decorative components having an elastomeric outer layer.Initially, the mold surface may be coated with a known mold releaseagent by means of a spray gun in order to facilitate the eventualdemolding of the resultant decorative object. By way of non-limitingexample, the mold release agent may be a composition includingsilicones, soaps, waxes and/or solvents.

Alternatively, or in addition to the application of the mold releaseagent, the mold cavity may be coated with a coating composition having apredetermined color utilizing a spray gun. The coating composition,otherwise referred to herein as an in mold coating may be selected froma variety of water and solvent bome solutions. For example, the coatingmay be a one or multi-component composition based on enamel or urethanecoating compositions, the latter being particularly preferred.

Among the numerous commercially available coating compositions whichhave proven useful are those marketed under the following trade names:Protothane® which is available from Titan Finishes Corp.; Polane® whichis available from Sherwin Williams, Inc.; and Rimbond® which isavailable from Lilly Corp., by way of non-limiting example.

The aromatic elastomer composition is preferably mixed by impingementmixing with or without the additional mixing achieved by the use ofsubsequent static mixers and is applied over the mold release agentand/or coating composition if present and, in the absence thereof,directly to a surface of the mold cavity by means of a spray gun orother spraying device to form the elastomeric outer layer. Dependinglargely on the intended use of the resulting decorative object, thethickness of the elastomeric outer layer is between about 0.2 and 3.0 mmand preferably between about 0.3 mm and 1.2 mm. Further, the elastomericlayer will preferably have a density of less than 1000 kg/M³, a Shore Adurometer hardness of less than 86, a tensile strength of greater than8.8 MPas and a tear strength of greater than 40 kn/m.

After applying the aromatic elastomer composition to the surface of themold cavity, a polyurethane foam composition may be injected into themold cavity to form a backing layer on the elastomer outer layer.Alternatively, the polyurethane foam composition may be applied by spraycoating the elastomer prior to or after removing the elastomeric layerfrom the mold.

The polyurethane foam composition can be tailored to meet the customer'srequirements in terms of density, crush resistance and other importantcharacteristics. As such, the foam's density can be controlledindependent of the elastomeric outer layer which is not true with regardto integral skin foams.

Polyurethane foam compositions which are considered useful for forming abacking layer on the elastomer outer layer include those disclosed inU.S. Pat. Nos. 4,389,454 and 5,512,319, which are hereby expresslyincorporated by reference. The spray processing parameters of thepresent invention will generally fall within specific ranges to insurethe quality of the resulting components. For example, it is preferredthat the mold and elastomer composition temperatures each be maintainedat from about 25° C. to about 85° C., with a range of 55° C. to 70° C.being preferred. Likewise, the chemical pressures as the elastomericcomposition enters the spray gun should be between about 48 to about 140bar, with a range of 60 to 100 bar being preferred. The throughput isgenerally between 5 g/sec to about 100 g/sec, with 10 g/sec to 30 g/secbeing preferred. Each of the foregoing processing parameters work bestfor elastomeric compositions having viscosities up to 4000 cps at 25°C., with the viscosities more preferably ranging from 10 to about 2000cps at 25° C.

The working examples set forth in Table I below illustrate the mannerand process of making and using the invention and set forth thecurrently known best mode contemplated by the inventors of carrying outthe invention, however the examples are not to be construed as limiting.

Polyol A is a glycerine initiated polyether polyol including propyleneoxide and ethylene oxide, having a hydroxyl number of 35 and a numberaverage molecular weight of approximately 4800. Polyol B is adipropylene glycol initiated polyether polyol, including propylene oxideand ethylene oxide having number 29 and a number average weight ofapproximately 3800. Polyol C is a graft polyol having 50% solids (1:1acrylonitrile:styrene acrylonitrile) dispersed in a trimethylolpropaneinitiated polyether polyol. Polyol D is a linear poly(ethylene glycol1,4-butanediol adipate initiated polyester polyol), having a hydroxylnumber of 55. Polyol E is a polytetrahydrofuran polyether polyol, havinga hydroxyl number of 110. Bicat ® is a bismuth neodecanoate/zincneodecanoate catalyst including 8.0 percent bismuth and 8.0 percentzinc. Dabco ® 33LV is a 33 percent triethylenediamine, 67 percentdipropylene glycol catalyst. Anti-foam A is a amorphous silica. defoamerPolycat ® 17 is a trimethylaminopropyl ethanolamine catalyst. Reactint ®brown is an organic dye. 2222 dye Fomrez ® UL-32 is a dioctyl tindimercaptide catalyst. Plasticolors is a pigment master batch including45.67 percent Brown 31368 Polyol B. Plasticolors is a pigment masterbatch containing 60 percent DM-45791X Polyol B, 12 percent Tinuvin ®770DF, 12 percent Tinuvin ® 328. Tinuvin ® is a hindered amine lightstabilizer: bis(2,2,6,6- 770DF tetramethyl-4-piperidinyl)decanedioate.Dabco ® EG is 25 percent triethylenediamine, 75 percent ethylene glycolcatalyst. Dabco ® HB is a 33 percent triethylenediamine, 67 percent 1,4butanediol catalyst. Isocyanate A s a prepolymer including 87.0 weightpercent diphenylmethane diisocyanate, 8.0 weight percent dipropyleneglycol, 5.0 weight percent polyether diol and having a percent NCO of23. Isocyanate B is a prepolymer including 56 weight percentdiphenylmethane diisocyanate, 38 weight percent Polyol D, 6 percentcarbodiimide modified diphenyl- methane diisocyanate, 0.003 weightpercent benzoyl chloride, having a percent NCO of 19. LK-221 surfactantis a non-ionic surfactant.

Sample Sample Sample Sample Sample Resin 1 2 3 4 5 System #1 SprayedSprayed Sprayed Cast Cast Isocyanate A 52.2 50 86 60.6 Isocyanate B 61.2Polyol A 70.36 38.04 66.55 Polyol B 13.3 30 58.78 Polyol C 20 Polyol D15 93.98 Polyol E 30.0 1,4 butanediol 10 10 10 chain extender Ethyleneglycol 12 5 chain extender LK-221 surfactant 1.5 Bicat ® 8 catalyst 0.040.06 Dabco ® 33LV catalyst 1 1.5 Polycat ® 17 catalyst 0.5 Fomrez ®UL-32 0.05 0.02 catalyst Dabco ® EG catalyst 1.2 0.2 Dabco ® HB 1.0Anti-foam A defoamer 0.1 0.1 Molecular sieve water 1 1 0.7 scavengerPlasticolors DM-45791X 4.2 brown UV pigment Reactint ® brown 0.3 2222dye Plasticolors brown 3 31368 pigment Properties from Sprayed SkinDensity (kg/m³) 945 956 949 1086 1009 Shore A Hardness 72 77 86 70 80Heat aged shore A hard. 78 87 (500 hrs., 121 C.) Tensile Strength (MPa)8.8 18.9 16.5 25.1 13.2 Heat Aged Tensile 8.1 16.4 19.4 Strength (500hrs., 121 C.) Elongation at Break (%) 208 400 260 756 379 Heat AgedElongation 344 605 336 (500 hrs, 121 C.) Die C Tear Strength 40 49.9 5963 47.8 (kN/m) Heat aged die C tear str. 58.5 69 (500 hrs., 121 C.)

What is claimed is:
 1. A sprayable elastomer composition for formingdecorative components having an elastomeric outer surface, saidcomposition comprising: the reaction product of: a) an aromaticisocyanate composition; b) a solids containing polyol including up toabout 60.0 weight percent solids and selected from the group consistingof graft polyols, polyisocyanate polyaddition polyols, polymer polyols,PHD polyols, and mixtures thereof; c) a polyol composition including atleast one polyol other than b) selected from the group consisting ofpolyether, low unsaturation polyether, polyester, polytetrahydrofuran,amine functional polyols and mixtures thereof, said polyol having atheoretical number average molecular weight of from about 3,800 to about10,000; d) optionally one or more components selected from the groupconsisting of catalysts, chain extenders, defoamers, surface-activeagents, adhesion promoters, flame retardants, anti-oxidants, waterscavengers, dyes, ultraviolet light stabilizers, pigments, fillers,thixotropic agents and mixtures thereof.
 2. The sprayable elastomer ofclaim 1 wherein the solids content of all components other than a) is upto 40.0 weight percent.
 3. The sprayable elastomer of claim 1 whereinsaid aromatic isocyanate composition is selected from the groupconsisting of pure dipheylmethane diisocyanate, diphenylmethanediisocyanate prepolymer, carbodiimide-uretonimine modifieddiphenylmethane diisocyanate and mixtures thereof.
 4. The sprayableelastomer of claim 1 wherein b) is present in an amount of between about5.0 weight percent to about 70.0 weight percent based on the total ofall components other than a).
 5. The sprayable elastomer of claim 1wherein said elastomer has a sprayed thickness upon curing of betweenabout 0.2 mm to about 3.0 mm.
 6. The sprayable elastomer of claim 1wherein said elastomer has a density of less than 1000 kg/m³ afterspraying.
 7. The sprayable elastomer of claim 1 wherein elastomer has ahardness upon curing of less than or equal to 86 Shore A.
 8. Thesprayable elastomer of claim 1 wherein said elastomer has a tensilestrength upon curing of at least 8.0 MPa.
 9. The sprayable elastomer ofclaim 1 wherein the isocyanate index ranges from about 80 to about 120.10. The sprayable elastomer of claim 1 wherein said elastomer includes abismuth catalyst.
 11. A sprayable elastomer composition for formingdecorative components having an elastomeric outer surface, saidcomposition comprising: the reaction product of: a) an aromaticisocyanate; b) a polyol composition including one or more polyolsselected from the group consisting of polyether, low unsaturationpolyether, polyester, polytetrahydrofuran, amine functional polyols andmixtures thereof, said polyol having a theoretical number averagemolecular weight of from about 3,800 to about 10,000, and a secondpolyol selected from the group consisting of graft polyols,polyisocyanate polyaddition polyols, polymer polyols, PHD polyols, andmixtures thereof, wherein the solids content of the second polyol is upto about 60.0 weight percent solids; c) optionally one or morecomponents selected from the group consisting of catalysts, chainextenders, defoamers, surface-active agents, adhesion promoters, flameretardants, anti-oxidants, water scavengers, dyes, ultraviolet lightstabilizers, pigments, fillers, thixotropic agents and mixtures thereof;wherein said elastomer has an elongation after heat aging at 121° C. for500 hours of at least 150 percent.
 12. The sprayable elastomer of claim10 wherein said catalyst includes an organo-metallic catalyst.
 13. Thesprayable elastomer of claim 10 wherein said elastomer includes abismuth catalyst.
 14. The sprayable elastomer of claim 10 wherein anultraviolet light stabilizer is present in an amount ranging from 0.25weight percent to 0.75 weight percent based on the total of allcomponents other than a).
 15. The sprayable elastomer of claim of claim10 wherein said elastomer has a sprayed thickness upon curing of betweenabout 0.2 mm to about 3.0 mm.
 16. The sprayable elastomer of claim 10wherein said elastomer has a density of less than 1000 kg/m³ afterspraying.
 17. The sprayable elastomer of claim 10 wherein elastomer hasa hardness upon curing of less than or equal to 86 Shore A.
 18. Thesprayable elastomer of claim 10 wherein said elastomer has a tensilestrength upon curing of at least 8.0 MPa.
 19. An elastomeric articlecomprising: the reaction product of: a) an aromatic isocyanatecomposition; b) a solids containing polyol including up to about 60.0weight percent solid and selected from the group consisting of graftpolyols, polyisocyanate polyaddition polyols, polymer polyols, PHDpolyols, and mixtures thereof; c) a polyol composition including atleast one polyol other than b) selected from the group consisting ofpolyether, low unsaturation polyether, polyester, polytetrahydrofuran,amine functional polyols and mixtures thereof, said polyol having atheoretical number average molecular weight of from about 3,800 to about10,000; d) optionally one or more components selected from the groupconsisting of catalysts, chain extenders, defoamers, surface-activeagents, adhesion promoters, flame retardants, anti-oxidants, waterscavengers, dyes, ultraviolet light stabilizers, pigments, fillers,thixotropic agents and mixtures thereof.
 20. An elastomeric articlecomprising: an in-mold paint; and an elastomeric skin, wherein said skincomprises the reaction product of: a) an aromatic isocyanate; b) apolyol composition including one or more polyols selected from the groupconsisting of polyether, low unsaturation polyether, polyester,polytetrahydrofuran, amine functional polyols and mixtures thereof, saidpolyol having a theoretical number average molecular weight of fromabout 3,800 to about 10,000, and a second polyol selected from the groupconsisting of graft polyols, polyisocyanate polyaddition polyols,polymers polyols, PHD polyols, and mixtures thereof, wherein the solidscontent of the second polyol is up to about 60.0 weight percent solids;c) optionally one or more components selected from the group consistingof catalysts, chain extenders, defoamers, surface-active agents,adhesion promoters, flame retardants, anti-oxidants, water scavengers,dyes, ultraviolet light stabilizers, pigments, fillers, thixotropicagents and mixtures thereof; wherein said elastomer has an elongationafter heat aging at 121° C. for 500 hours of at least 150 percent.